Sustainable, facile separation of the molten carbonate electrolysis cathode product

ABSTRACT

A process for the separation of electrolyte from the carbon in a solid carbon/electrolyte cathode product formed at the cathode during molten carbonate electrolysis. The processes allows for easy separation of the solid carbon product from the electrolyte without any observed detrimental effect on the structure and/or stability of the resulting solid carbon nanomaterial.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/667,387, filed Oct. 29, 2019, which claims the benefit of U.S.Provisional Application No. 62/752,141, filed Oct. 29, 2018. The entirecontent of those applications are hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to an improved process for the separationof electrolyte from the carbon in a solid carbon/electrolyte cathodeproduct formed at the cathode during molten carbonate electrolysis. Theprocesses described herein allow for easy separation of the solid carbonproduct from the electrolyte without any observed detrimental effect onthe structure and/or stability of the resulting solid carbon product.

BACKGROUND OF THE INVENTION

One way to ameliorate the adverse consequences of rising carbon dioxidelevels is by transforming carbon dioxide into a useful product. Variousprocesses have been described to transform carbon dioxide to carbonnanomaterials, such as carbon nanotubes, carbon nanofibers, carbonnano-onions, carbon scaffolds, carbon platelets, and graphene, by moltencarbonate electrolysis (see, e.g., citations 1-6 listed herein). Forexample, carbon nanotubes may be formed by electrolysis in moltenlithium carbonate (melting point 723° C.) or in related mixes includingalkali or alkali earth carbonates, with or without oxides, borates,phosphates, sulfates, nitrates, chlorides or other inorganic salts.During this electrolysis, the carbon nanomaterials are typicallydeposited on the electrolysis cathode but are bound to the cathode withan excess of electrolyte.

Some processes explored to separate the carbon from the carbonateelectrolyte in the resulting product include a variety of aqueous washesor drawing the molten electrolyte through a mesh with a BNZ (calciumaluminum silicate) firebrick (see, e.g., citation 2). The aqueouswashing methodologies require cooling and heat is reversibly lost fromthe electrolysis cell. Both the aqueous and molten firebrick extractionconsumes large amounts of material, which is detrimental tosustainability of the overall carbon dioxide removal process. Forexample, the aqueous separations may be accomplished by the addition ofcopious amounts of water and additives such as ammonia sulfate, orformic or hydrochloric acid to facilitate dissolution of the carbonateinto the aqueous phase for separation from the solid carbon product. Forthe (molten) solid carbon/electrolyte product the firebrick acts to drawthe molten carbon electrolyte by chemical reaction with the aluminate orsilicate component of the firebrick. These firebrick components areconsumed during the separation, such as without being bound by anytheory or specific equation, the reaction of lithium carbonate consumingfirebrick materials exemplified by the consumption of alumina, andsilicon dioxide respectively to lithium aluminate and lithium ortho ormeta silicate:

Li₂CO₃+Al₂O₃→2LiAlO₂+CO₂(gas evolved)  (1)

2Li₂CO₃+SiO₂→Li₄SiO₄+2CO₂(gas evolved)  (2a)

Li₂CO₃+SiO₂→Li₂SiO₃+CO₂(gas evolved)  (2b)

Carbon nanotubes are flexible and have the highest tensile strength ofany material measured to date (see, e.g., citations 7 and 8 listedherein). Recently, it has been observed that the carbon product ofmolten carbonate electrolysis can consist of a matrix of intermingledcarbon nanotubes (see, e.g., citation 2 listed herein).

There is therefore a need for new and efficient processes to separateelectrolyte from the solid carbon nanomaterial formed at the cathodeduring electrolysis, thereby providing a more sustainable (e.g.,preventing heat and electrolyte waste), more cost-effective process andproviding a cleaner, more useful nanomaterial.

SUMMARY OF THE INVENTION

The present invention relates to an improved process for the separationof the carbon product from a solid carbon/molten electrolyte mixedproduct (a carbanogel) formed, e.g., on the cathode, during a carbonateelectrolysis reaction.

A variety of carbon nanomaterials can be deposited on the cathode bycontrol of the electrolysis conditions. During deposition, the carbonformed at the cathode exhibits a strong affinity for electrolyte, andthe cathode product contains a mix of solid carbon and moltenelectrolyte. The deposited cathode product is a paste or gel attemperatures above the melting point of the electrolyte, or when thecathode is removed and allowed to cool to room temperature, the cathodeproduct is a solid mixture of the carbon and congealed electrolyte. Ineither case, the cathode deposition contains a majority of electrolyteby mass compared to carbon. The solid carbon product/electrolyte mix isspontaneously formed on the cathode in real time during theelectrolysis, and not after the solid carbon is formed. Solid product isnot dislodged from the cathode to subsequently form a slurry with theelectrolyte. The paste is black in color (and red hot) and is clearlydistinguished from the clear molten electrolyte between the electrodesand in the electrolysis chamber. The product is a thick paste layer onthe cathode which grows as the electrolysis continues. Depending on theelectrolysis conditions, the percentage of electrolyte in the pastewhich contains the cathode product ranges from 70 to 97 percent byweight and is typically in the range from 90 to 97 percent by weight.

The present inventor has surprisingly found that the solid carbonproduct can be separated from a solid carbon/molten electrolyte mixedproduct (carbanogel) by a compression process, and that carbanogelsformed on the cathode during a molten carbon carbonate electrolysisreaction can be repeatedly compressed without any observed detrimentaleffect on the structure and/or stability of the resulting solid carbonnanomaterial, thereby allowing for efficient separation of the desiredsolid carbon product.

Typically, individual carbon nanomaterials have a diameter of less than500 nm. The present inventor has also surprisingly found that carbonnanotubes comprising a matrix of highly porous, intermingled carbonnanotubes that are greater than, for example, 500 nm height, can berepeatedly compressed to a small fraction of their initial volumewithout damage the structure of the carbon nanomaterials (see, e.g.,citations 9-11 listed herein).

Typically, the desired carbon product develops as a thick paste on thecathode (it is not released into the free, circulating electrolyte)during the electrolysis reaction. The paste comprises solid carbonproduct and bound electrolyte. In the processes described herein, thepaste containing solid carbon product is separated from the boundelectrolyte. The electrolyte in the paste is stationary and is separatefrom the free electrolyte situated in the electrolysis chamber.

In one aspect, the present invention relates to a process for preparinga solid carbon product. In one embodiment, the process comprisesseparating electrolyte from a solid carbon/molten electrolyte mixedproduct (a “carbanogel”) formed during a carbonate electrolysis. In oneembodiment, the process comprises:

-   -   (i) applying a force to a solid carbon/molten electrolyte mixed        product to remove the electrolyte;    -   (ii) removing the force; and    -   (iii) optionally, isolating the solid carbon product.

In one embodiment of any of the processes described herein, steps (i)and (ii) are repeated one or more times, such as two, three or fourtimes, prior to step (iii).

In certain embodiments of any of the processes described herein, theforce (compression) is applied manually, pneumatically or hydraulically.

In certain embodiments of any of the processes described herein, theforce (compression) is conducted at a pressure of between about 10 psiand about 100,000 psi, such as between about 50 psi and about 50,000psi, or between at about 100 psi and about 1,000 psi.

In certain embodiments of any of the processes described herein, theelectrolyte is removed through an interface with pores, such as, forexample, a filter, a porous carbon felt, a graphite felt, a metal mesh,a porous or sieve ceramic, or any combination thereof.

In one embodiment, the pore size of the interface is smaller than thesolid carbon matrix product size. For example, the pore size of theinterface may be between about 10 μm and about 10 mm, such as betweenabout 50 μm and about 5 mm or between about 70 μm and about 3 mm.

In one embodiment of any of the processes described herein, the processin conducted in vacuo (i.e., by applying a vacuum during theseparation/extraction process). In one embodiment, the vacuum enhancesremoval of the electrolyte and separation of the solid carbon product.

In one embodiment of any of the processes described herein, the vacuumapplied is between about 0.1 and about 0.9 atmospheres.

In another embodiment of any of the processes described herein, thevacuum applied is greater than about 0.8 atmospheres, or greater thanabout 0.9 atmospheres, such as between about 0.8 and about 0.999atmospheres, or between about 0.9 and about 0.99 atmospheres.

In another embodiment of any of the processes described herein, theprocess is conducted at a pressure between about 0.1 and about 0.9atmospheres, such as between about 0.2 and about 0.9 atmospheres.

In another embodiment of any of the processes described herein, theprocess is conducted at a pressure less than about 0.1 atmospheres, suchas less than about 0.01 atmospheres.

In one embodiment of any of the processes described herein, the vacuumapplied is between about 0.01 MPa and about 0.1 MPa, such as betweenabout 0.05 MPa and about 0.1 MPa, such as about 0.09 MPa.

In another embodiment of any of the processes described herein, theprocess is conducted in the absence of oxygen, for example, under ablanket of gas that is free or substantially free of oxygen (an oxygenexcluding gas). For example, in one embodiment, the oxygen excluding gasblankets the mixed product to protect the solid carbon product fromoxidation.

In certain embodiments, the oxygen excluding gas is an inertnon-oxidizing gas, such as, for example, nitrogen, carbon dioxide,argon, or a reducing gas, such as, for example, methane, ammonia,hydrogen and hydrogen sulfide, and any combination of any of theforegoing.

In another embodiment of any of the processes described herein, theprocess is conducted at a temperature between about 399° C. and about900° C., such as between about 700° C. and about 900° C. In anotherembodiment of any of the processes described herein, the process isconducted at a temperature of about 399° C., about 723° C. or about 891°C., which correspond, respectively, to the melting points of eutecticlithium sodium potassium carbonate, lithium carbonate, and purepotassium carbonate.

In another embodiment of any of the processes described herein, themixed product is cooled to below the point of solidification, such asbelow 700° C., after its formation by electrolysis and thenreheated/melted prior to the one or more compression step(s) in theprocesses described herein.

In other embodiments of any of the processes described herein, the solidcarbon/molten electrolyte mixed product is compressed directly on thecathode in the electrolysis chamber.

In one embodiment of any of the processes described herein, the solidcarbon/molten electrolyte mixed product is removed from the cathode.

In another embodiment of any of the processes described herein, thesolid carbon/molten electrolyte mixed product is removed from thecathode in the electrolysis chamber, e.g. without pumping, into aseparate extraction compression chamber prior to separation of the solidproduct.

In another embodiment of any of the processes described herein, theprocess does not involve a flowing electrolyte.

In another embodiment of any of the processes described herein, theprocess does not involve a recirculation loop.

In another embodiment of any of the processes described herein, theresulting solid carbon product has an average thickness greater than 10μm, such as greater than 0.3 mm, greater than 1 mm or greater than 3 mm.

In another embodiment, of any of the processes described herein, theresulting solid carbon product comprises greater than about 80% carbonnano-materials, such as greater than about 85%, greater than about 90%or greater than about 95% carbon nano-materials.

In a preferred embodiment, the carbon nano-materials are carbonnanotubes, carbon nano-onions, carbon nano-platelets, carbonnano-scaffolds, graphene or any combination thereof.

In another embodiment, of any of the processes described herein, amorphological template is not present on the cathode during formationand/or separation (compression) of the solid carbon/molten electrolytemixed product.

In another aspect, the present invention relates to a chamber useful forconducting any of the process described herein.

In one embodiment, the present invention relates to an extractionchamber for separating electrolyte from a solid carbon/moltenelectrolyte mixed product formed during a carbonate electrolysis, theextraction chamber comprising

-   -   (i) a solid carbon/molten electrolyte mixed product formed        during a carbonate electrolysis;    -   (ii) a compression device compressing the solid carbon/molten        electrolyte mixed product;    -   (iii) a removal device configured to remove the compression;    -   (iv) an interface with pores through which electrolyte separated        from the mixed product during compression is collected; and    -   (v) optionally, a vacuum applied to the extraction chamber.

In one embodiment, the extraction chamber is rectangular or circular.

In one embodiment, the extraction chamber is operated in the verticalmode.

In one embodiment, the extraction chamber is operated in the horizontalmode.

In one embodiment, the extraction chamber is operated in an angularmode.

In one embodiment, the extraction chamber is operated within a kiln.

In one embodiment, the extraction chamber is situated with anelectrolysis chamber.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a block diagram showing separation at the cathode in anelectrolysis chamber of electrolyte from the solid carbon in the solidcarbon/electrolyte cathode product of a molten carbonate electrolysisreaction.

FIG. 1B is a block diagram showing separation in an extraction chamber(not at the cathode in an electrolysis chamber) of electrolyte from thesolid carbon in the solid carbon/electrolyte cathode product of a moltencarbonate electrolysis reaction.

FIGS. 2A-2E show various shapes of suitable extraction chambers for usein the processes described herein.

FIG. 3A shows exemplary rectangular extraction chambers for use in theprocesses described herein.

FIG. 3B shows exemplary circular extraction chambers for use in theprocesses described herein.

FIG. 3C shows an exemplary extraction chamber for use in the processesdescribed herein operating in the vertical mode.

FIG. 3D shows an exemplary extraction chamber for use in the processesdescribed herein operating in the horizontal mode.

FIG. 4A-4E show an exemplary extraction chamber for collecting rawmaterial from an electrode in accordance with the processes describedherein, with the extraction chamber positioned at an angle and directlyinterfaced to the electrolysis chamber.

FIG. 5 shows an exemplary extraction chamber for use in the processesdescribed herein that can be operated with or without a vacuum system toseparate the electrolyte in vacuo.

FIGS. 6A-6C show pressure being applied to extraction chamber for use inthe processes described herein by mechanical, pneumatic or hydraulicpressure. The extraction unit is inside the kiln.

FIGS. 7A-7H show an exemplary product extractor situated within theelectrolysis chamber and an extraction process.

DETAILED DESCRIPTION OF THE INVENTION

In describing the illustrative, non-limiting embodiments of theinvention illustrated in the drawings, specific terminology will beresorted to for the sake of clarity. However, the invention is notintended to be limited to the specific terms so selected, and it is tobe understood that each specific term includes all technical equivalentsthat operate in similar manner to accomplish a similar purpose. Severalembodiments of the invention are described for illustrative purposes, itbeing understood that the invention may be embodied in other forms notspecifically shown in the drawings.

U.S. Publication Nos. 2019/0039040 and 2018/0044183, which are herebyincorporated by reference in their entireties, describe the synthesis ofcarbon nanomaterials via electrolysis in carbonate containing moltenelectrolytes.

As used herein, the term “carbanogel” refers to a product analogous toan aerogel in which the air in the aerogel is replaced by moltencarbonate. For example, a carbanogel contains a majority of moltencarbonate with an intermingled solid matrix component. For sustainable,effective carbon dioxide splitting the electrolyte trapped in thecarbanogel product of molten carbonate electrolysis needs to beseparated to be available for continued use in the electrolysis.

As used herein, a gas that is “substantially free of oxygen” means a gasthan contains less that about 1000 ppm of oxygen, such as less thanabout 500 ppm, less than about 400 ppm, less than about 300 ppm, lessthan about 200 ppm, less than about 100 ppm, less than about 50 ppm,less than about 25 ppm, less than about 10 ppm, less than about 5 ppm,or less than about 1 ppm, of oxygen.

FIG. 1A is a diagram of an exemplary extraction system 100 thatseparates electrolyte from solid carbon in the solid carbon/electrolyteproduct formed at the cathode during a molten carbonate electrolysisreaction. The system 100 includes a force applicator 102, a solidcarbon/electrolyte product 104, a cathode 106, a filter or interfacewith pores 108, and an electrolyte 110 pressed out of the solidcarbon/electrolyte product. Although the interface with pores 108 isshown on the side of the solid carbon electrolyte product 104 in oneembodiment of FIG. 1A, it is to be understood that the interface withpores 108 alternatively can be an integral part of the cathode, if thecathode comprises a porous material, in which case the pressedelectrolyte 110 is then pushed through and out the backside of thecathode 106.

More specifically, the system 100 can be a chamber, such as anextraction chamber. The chamber 100 can be formed as a single unitaryhousing or container 101 having an interior. As shown, the container 101can be elongated with a bottom, two transverse sides or walls and twolongitudinal sides or walls that have a substantially rectangular crosssection and define a central longitudinal axis (extending along a lengthof the container 101), though any suitable shape and size can beutilized. The top of the container 101 is open, though a cover withholes can optionally be placed over at least two side sections 101 a,101 c of the container 101. The transverse walls extend substantiallyorthogonal to the longitudinal axis and the longitudinal sides extendsubstantially parallel to the longitudinal axis.

One or more dividing panels or separators, such as filters, membranes orinterfaces are received in the interior of the container 101. Here, afirst interface 108 a has a first side and a second side opposite thefirst side. The first side of the first interface 108 a faces onetransverse side of the container 101 to define a first section 101 a ofthe interior of the container 101 between the first side of the firstinterface 108 a and the transverse side of the container 101. A secondinterface 108 b has a first side and a second side opposite the firstside. The first side of the second interface 108 b faces the second sideof the first interface 108 a to define a second section 101 b of theinterior of the container 101 between the first side of the secondinterface 108 b and the second side of the first interface 108 a. Thesecond side of the second interface 108 b faces the other transverseside of the container 101 to define a third section 101 c of theinterior of the container 101 between the second side of the secondinterface 108 b and the other transverse side of the container 101. Thecenter section 101 b forms an extraction chamber or container, and thetwo side sections 101 a, 101 c each form a collection chamber orcontainer.

As shown, each section 101 a, 101 b, 101 c can have a substantiallysquare cross section, though any suitable shape and size can beutilized. The interfaces 108 are relatively thin and can form a plate(or two plates with filter material therebetween) with two oppositesides that are relatively flat and planar and can have multiple holesthat allow material to pass from the center section 101 b to one of thetwo outer sections 101 a, 101 c through the interface 108. Theinterfaces 108 extend substantially transverse to the longitudinal axisof the container across the entire width and height, and parallel to thetransverse sides of the container 101, so that material in the centersection 101 b cannot pass to the outer sections 101 a, 101 c, exceptthrough one of the two interfaces 108 a, 108 b. The interfaces 108 a,108 b can be any suitable device that separates material. Each section101 a, 101 b, 101 c has a respective interior space of the interior ofthe container 101.

The middle or center section 101 b of the container 101 receives theforce applicator 102, the cathode 106, and the material 104, such as acarbon/electrolyte product. The force applicator 102 is sized and shapedto the center section 101 b, here shown as a compressor formed by a flatsquare or rectangular plate that extends the entire space between thetwo interfaces 108 a, 108 b and the two longitudinal sides of thecontainer 101. The cathode 106 can also be a flat square or rectangularplate that extends the entire space between the two interfaces 108 a,108 b and the two longitudinal sides of the container 101. The cathode106 can be situated, for example at the bottom of the interior space ofthe center section 101 b.

As illustrated by the large arrows in FIG. 1A, the cathode 106 andmaterial 104 is placed in the center section 101 b. The compressor 102is located above the center section 101 b and is forced downward intothe center section 101 b, such as by pneumatic operation. As thecompressor 102 moves downward, it forces product 104 to separate. Thefirst interface 108 a can have a first filter mechanism (e.g., firstporous material) that filters a first product (i.e., gas, liquid ormaterial), and the second interface 108 b can have a second filtermechanism (e.g., second porous material) that filters a second product(e.g., gas, liquid or material) which is the same or different from thefirst product. Here, both the first and second interfaces 108 a, 108 bfilter carbon so that only an electrolyte 110 can pass through theinterfaces 108 a, 108 b into the first and second sections 101 a, 101 c,respectively. As noted, the compressor 102 is sized and shaped to matchthe size and shape of the center section 101 b so that material 104doesn't escape around the sides of the compressor 102 as it compressesdownward, but instead the material 104 presses through the interfaces108 a, 108 b.

In a further embodiment, an oxygen excluding gas (e.g., a gas that isfree or substantially free of oxygen) 112 may optionally be used toblanket (e.g., completely cover) the system 100, for example, to preventoxidation of the solid carbon during electrolyte separation from thesolid carbon/electrolyte product 104. In this embodiment, the system 100can include a main housing that encloses the compressor 102 and thecontainer 101, such as shown for example in FIGS. 2A-2C (see., e.g.,main housing 201). The gas 112 can be pumped into the main housingaround the container 101 to contact the product 104 and/or electrolyte110 in any of the sections 101 a, 101 b, 101 c.

The chamber 100 of FIG. 1A has sections 101 a, 101 b, 101 c arranged ina side-by-side relationship, and with electrolyte being filtered intothe two outer sections 101 a, 101 c. However, the sections 101 can bearranged in any suitable manner, and only a single section (orcompartment) is needed to hold the product 104 and another section (orcompartment or container) is needed to receive the filtered electrolyte110.

FIG. 1B is a diagram of an exemplary system 200 that separateselectrolyte from solid carbon in a solid carbon/electrolyte product inan extraction chamber. Using similar components as labeled in FIG. 1A,the solid carbon/electrolyte product 104 is first removed from thecathode of the electrolysis chamber (not shown) and placed as a gel(hot) or initially solid (frozen gel, then reheated to a molten gel)into the electrolyte pressing extraction reservoir or chamber 210. As afurther embodiment, an optional vacuum 220 can be applied to thepressing chamber to provide a pull of electrolyte through the interfacewith pores 108.

More specifically, the extraction chamber 200 has a housing 202 withfour sides or walls 204 forming a container with an interior space and asquare or rectangular cross section. The housing 202 has an open top andan open bottom. The interface 108 is provided at the bottom of thehousing 202 and closes the open bottom of the housing 202. Product 104is placed in the interior of the housing 202. The lower container orextraction chamber 210 is located beneath the housing 202 and interface108. The compressor 102 is sized and shaped to match the size and shapeof the interior of the housing 202, and pushes downward on the product104, forcing electrolyte through the interface 108 and into theextraction reservoir, such as a square or rectangular chamber 210. Inaddition, an optional vacuum 220 can be provided with or instead of thecompressor 102 to further facilitate electrolyte passing through theinterface 108; though it is also noted that some electrolyte may passthrough the interface 108 by force of gravity without the use of acompressor 102 and/or vacuum 220. The vacuum 220 can also operate as adrain to collect separated electrolyte, or a separate drain (e.g., ahose or line) can be provided. The interface 108 prevents carbon frompassing, so only electrolyte enters the extraction chamber 210. Thoughnot shown, a cathode 106 can also be located in the housing 202.

FIGS. 2-6 show other embodiments of the invention. The system can haveany suitable size or shape and be configured vertically, horizontally orat an angle. Turning to FIGS. 2A, 3D, a horizontal configuration of theextractor system 300 is shown. The system 300 has an extractioncontainer or chamber 302, an electrolyte collection chamber 310, and afilter 308 between the container 302 and the collection chamber 310. Theextraction chamber 302 has a top, bottom and at least two sides orwalls, here shown as longitudinal walls extending along the length ofthe chamber 302. One side can be open to receive the plate of thecompressor 102. In the embodiment shown, the chamber 302 is elongatedand the compressor 102 is received at an open proximal transverse end ofthe chamber 302. The compressor 102 extends along the longitudinal axisof the chamber 302 from a proximal end of the chamber 302. Raw product304 can enter through an opening in a side wall or the top.

The interface or filter 308 is located at the open distal transverse endof the extraction chamber 302, and the collection chamber 310 isconnected to the distal transverse end of the extraction chamber 302. Aheat zone 306 can be provided at a portion of the container 300, such asat a proximal portion and immediately adjacent to the interface orfilter 308. The compressor 102 pushes inward from the proximal end tothe distal end so that heated product passes through the filter 308 andinto the electrolyte collection reservoir or chamber 310. The vacuum 320can be connected to the electrolyte collection reservoir 310 tofacilitate electrolyte passing through the filter 308 into the reservoir310. The vacuum 320 can be coupled on a side of the reservoir 310opposite the filter 308. The vacuum acts to both pull electrolyte fromthe carbon nanogel and to protect it from oxidations

As shown in FIGS. 2B, 2C, 3B, the compressor 102 and container 202 canbe circular, and FIGS. 2B, 2C, 3C show that the compressor 102 canengage or attach to a main housing 201. Turning to FIGS. 2D, 2E, thecontainer 202 can have a support shelf or ledge 205 extend inwardly fromone or more of the side walls 204. A steel support plate 212 can beplaced on the ledge 205. The support plate 212 has a plurality ofopenings, such as forming a honeycomb pattern. The plate 212 can supportan interface 208 that is placed on top of the plate 212, such as afiltering membrane, mesh screen, felt material or the like.

FIG. 3A shows a chamber 202 for use with a molten paste material from anelectrode that contains carbon product and electrolyte. The paste is ontop of a mesh screen 208 on a porous support 212. The compressor pushesdown on the paste and electrolyte passes through the mesh screen 208into a separate container or the bottom of the chamber. The chamber 202can be gas tight, and oxygen-free gas (e.g., Ar, N₂, CO₂) or a vacuumcan be applied inside the container around the paste material.

FIG. 3B shows that instead of an internal support ledge 205, a gratingsupport can be provided to support the porous mesh support 212. Inaddition, a mesh screen 208 can be provided on top of the mesh support212, and the sample is placed on top of the mesh screen 208. A heatercan be provided to heat the system, for example the system can be insidea kiln or coupled to a kiln.

FIGS. 2B, 2C show that the compressor 102 can be formed as a plate and athreaded bar. The threaded bar can extend through a threaded opening inthe top plate of the main housing 201 and the threaded bar can berotated in the opening to extend the bar and plate further into thecontainer 202. FIG. 3C shows another embodiment in which the compressor102 has a press plate and a scissor-type hydraulic jack mounted to thepress plate. The jack presses against the top plate of the main housing201, and a threaded bar in the jack can be rotated to extend the jackand move the press bar or rod and press plate further into the container202. FIG. 3C also shows a molten paste product in the container 202 fromthe electrode. The molten paste product contains carbon product andelectrolyte. The press plate forces electrolyte out of the pasteproduct, through a mesh screen 208 positioned on a porous support 212,into a collection reservoir at the bottom of the container 202. Inaddition, a divider 207 is provided in the main housing 207. The divider207 is a plate that extends across the main housing 201 and around thecompressor 102, such as the rod of the compressor 102. The divider 207forms a gas-tight seal and encloses the container 202. An oxygen-freegas can be introduced into the sealed enclosure. The gas comes intocontact with the product when the paste product from the electrode isintroduced prior to placement of the press plate, or during pressingthrough any leaks in the seal between the press plate and the pasteproduct from the electrode.

FIGS. 4A-4E show a collection chamber 450 positioned with respect to anelectrolysis chamber 400 and operating to remove product. In FIG. 4A,the electrolysis chamber 400 is shown with a cathode electrodepositioned between two anode electrodes, surrounded by electrolyte. Thecollection chamber 450 is integrally formed with our coupled to theelectrolysis chamber 400. The collection chamber 450 is above the levelof the electrolyte in the electrolysis chamber 400. A transportapparatus is coupled to the cathode, such as by a wire, bar or solidrod, and configured to move the cathode from the electrolysis chamber400 to the collection chamber 450. Here, the transport apparatusincludes a conveyor device that is located above the electrolysischamber 400 and the collection chamber 450. When carbon is attached tothe cathode, one or more transport motors are operated to verticallyraise the cathode out of the electrolysis chamber 400, FIG. 4B, and thenmove the cathode horizontally over the collection chamber 450, FIG. 4C.The compressor 452 is withdrawn from the collection chamber 450, and thecathode is lowered by the transport apparatus into an opening in thecollection chamber 450.

Raw product is then released from the cathode into the collectionchamber. For example, the collection chamber 450 can have one or morescraper blades 454 positioned in the opening of the collection chamber450. A scraper channel or opening is formed between the one or moreblades 454. The cathode is lowered into the scraper channel between thescraper blades 454, which forces the raw product off of the cathode andinto the collection chamber 450. The compressor then extends into thecollection chamber and compresses the raw product. Electrolyte from theproduct passes through the interface of the collection chamber andreturns directly into the electrolysis chamber, while carbon remains inthe collection chamber. The extracted carbon product is removed togetherwith the collection chamber. It is further noted that any of the systemsof FIGS. 1-3, 5-7 can be utilized for the collection chamber 450 ofFIGS. 4A-4E. in addition, while the collection chamber 450 is shown atan angle with respect to the electrolysis chamber 400, the collectionchamber 450 can be positioned vertically or horizontally with respect tothe electrolysis chamber 400.

FIG. 5 shows a product extractor or collection chamber 450 and vacuumsystem 456 in a vertical arrangement. A vacuum system 456 can optionallybe attached to the collection chamber 450. The collection chamber 450can be a container with walls, here shown as a cube with rectangular orsquare sides and an open bottom. The vacuum system 456 includes anextraction chamber 410, gasket or sealant 412, and vacuum line 420. Theextraction chamber 410 can be a container or reservoir that retainselectrolyte that is drawn out of the extractor 450. The extractionchamber 410 is shown as a cube with square or rectangular sides and anopen top. The seal 412 is provided at the top edge of the extractionchamber 410 and bottom edge of the collection chamber 450 to form anair-tight seal between the collection chamber 450 and the extractionchamber 410. The vacuum line 420 is coupled to the extraction chamber410 and in gas communication therewith. Once the seal is formed, thevacuum line 420 can create a vacuum or negative pressure in theextraction chamber 410, that in turn pulls electrolyte out of theproduct contained in the collection chamber 450. The extraction chamber410 can then be removed, the electrolyte emptied, and the extractionchamber replaced. The vacuum system 456 shown in FIG. 5 can be utilizedwith any of the systems 100, 200, 300 of FIGS. 1-4. The drain tube orpipe 458 drains accumulation of excess electrolyte that has beenseparated from the paste product from the electrode.

FIGS. 6A, 6B, 6C show the extraction chamber 200 having a verticalconfiguration. As noted above with respect to FIG. 3C, the extractionchamber 200 can be enclosed in a main housing 201 that forms a completeenclosure around the extraction chamber 200. FIGS. 6A, 6B, 6C show thatthe main housing 201 can be a frame 203 that extends over the extractionchamber 200. The frame 203 has two elongated vertical support membersand a horizontal cross-member connecting the two vertical members. Thevertical members can be fixed to the ground or to a horizontal base orplatform 209. The extraction chamber 200 can be positioned on the base209. As further shown in FIG. 6B, the extraction chamber 200 can belocated within a kiln to control the temperature in the extractionchamber 200. FIGS. 6A, 6C show the compressor 102 having a threaded rodattached to the frame cross-member and a press plate, and FIG. 6B showsthe compressor 102 having a scissor-type jack mechanism coupled to thecross-member of the frame 203. FIG. 6C also show round electrolyte froma product extraction unit.

FIGS. 7A-7H show yet another embodiment of the invention. Here, theextraction system 500 is shown. The system 500 includes an electrolysisand extraction chamber 502, transport assembly 520, housing 530, and acompressor and collection assembly 550. The electrolysis and extractionchamber 502 is a container having one or more vertical side walls 504, abottom, and a top that is at least partially open. The containerreceives an anode electrode, a cathode electrode, and a liquidelectrolyte that surrounds the anode and cathode. An opening 506 isprovided along the at least one wall 504, at a position above the levelof electrolyte in the chamber 502.

The housing 530 at least partly encloses the electrolysis chamber 502.Here, the housing 530 can be a frame having an elongated support framemember extending horizontally over the electrolysis chamber 500. Thesupport frame member can connect with other frame features, such asvertical support beams that are connected to a base, as in FIGS. 6A, 6B.

The transport assembly 520 is used to raise the cathode out of theelectrolyte to remove the raw product, and then lower the cathode backinto the electrolyte after the raw product is removed. That can beaccomplished by any suitable mechanism(s), such as for example a motor,a gear or wheel, and a line. The motor and rotational wheel can beconnected to the horizontal support frame 530. The line is coupled withthe wheel and the cathode. The motor is operated to rotate the wheel,which in turn raises and lowers the cathode. The anode can also beseparately connected to the transport assembly 520 by a separate lineand wheel and have a separate or shared motor.

The compressor and collection assembly 550 has an extension rod 552,press plate 554, press wall 556, and collection device 560. Theextraction assembly 550 is received in an opening 506 in the one or moreside walls of the electrolysis chamber 500, and the entirety of theextraction assembly 550 is positioned above the electrolyte in theelectrolysis chamber 500. The press plate 554 is positioned verticallyinside the electrolysis chamber 500, and the rod 552 extendshorizontally through the wall opening 506 to the exterior of theelectrolysis chamber 500. The press wall 556 is a vertical plate or wallwith a proximal end that is coupled to and extends downward from thehorizontal support frame member 530. The wall 556 has a distal end thatextends downward into the electrolysis chamber 500. In the embodimentshown, the distal end of the wall 556 stops above the electrolyte, sothat the wall does not touch the electrolyte at the bottom portion ofthe electrolysis chamber 500. The press wall 556 can have other supportmembers, such as horizontal beams that connect with the frame at thebottom end of the wall 556. The press wall 556 has two sides each with arespective opposite outwardly-facing surface. A first wall surface facestoward the compressor 550 and a second wall surface faces away from thecompressor 550. The first wall surface is aligned with and faces aninward facing surface of the press plate 554. The rod 552 moves thepress plate 554 horizontally forward and inward into the container 502toward the press wall 556. Of course, other suitable means can beprovided to move the press plate forward, such as a scissor-like jackpositioned on the wall of the container 502.

The collection device 560 is situated at the bottom end of the pressplate 554. As shown, the collection device 560 can be a shelf thatextends horizontally outward from the bottommost edge of the press plate560, substantially orthogonal to the inwardly facing surface of thepress plate 560. The collection device 560 is sized to collect carbon(graphene) that is removed from the cathode. The collection device 560can be received in a channel formed in the bottom end of the press plate560, or attached to the bottom edge of the press plate 560. However,other suitable collection means can be provided, for example thecollection device 560 need not be connected to the press plate 554, butinstead can be connected to the at least one chamber wall 504 of theelectrolysis chamber 502, and extend outward from the chamber wall 504and inwardly toward the press wall 556.

Starting at FIG. 7E, operation of the extraction system 500 begins withthe anode and electrode lowered by the transport mechanism 520 into theelectrolyte inside the electrolysis and extraction chamber 502. Thecompression rod 552 is fully receded so that the press plate 554 iswithdrawn and can be against the one or more walls 504. At that point,electrolysis begins. In FIG. 7F, gas is emitted from the reaction at theanode and product begins to accumulate on the cathode. In FIGS. 7G-7H,the reaction continues, and more and more paste product is formed on thecathode.

At FIG. 7H, the cathode is saturated with paste product. Accordingly,the motor of the transport assembly 520 is operated, and the cathode islifted out of the electrolyte, FIG. 7A. At this point, the cathode andpaste product are substantially aligned with, and parallel to, the firstsurface of the press wall 556 facing the press plate 554. The press wall556 is positioned between the cathode and the anode. Accordingly, thepaste product mostly accumulates on the side of the cathode that facesthe press wall 556. Once the cathode is full raised, the press rod 552is operated, moving the press plate 554 inwardly toward the press wall556, as shown by the arrow. In FIG. 7B, the press plate 556 contacts thecathode, which in turn applies a compression force to the paste product,forcing the paste product down along the press wall 556 between thepress wall 556 and the cathode.

The expelled product reaches the collection device 560. The collectiondevice 560 can be a plate with openings or pores and can have a meshscreen or other filter mechanism situated on the porous plate. Thedistal end of the collection device 560 can contact the press wall 556and/or extend under the press wall 556. The paste product expelled bythe compression enters the collection device 560, which collects cleanproduct (such as carbon or graphene), and allows clean electrolyte topass through and return to the bottom of the electrolysis chamber 502.When pressed, electrolyte is pressed and separated from the pastethrough the supported screen. At FIG. 7C, the clean electrolyte hasreturned to the electrolysis chamber 502, and the clean product is inthe collection device 560. At FIG. 7D, the press rod 552 is operated towithdraw the press plate 554 outward away from the press wall 556 andreturn to its initial position adjacent the chamber wall 504. Thetransport device then lowers the cathode back into the electrolyte forfurther electrolysis, and the clean product is removed from thecollection device 560.

It is further noted that when the paste product is removed from theelectrolyte, FIG. 7A, it will begin to cool and might solidify. A heatcan be applied during the compression, FIG. 7B, to facilitate separationof the carbon and electrolyte. In addition, a scraper can be utilized tofully remove product from the press plate surface and the surface of thecathode, FIG. 7D. And as shown, the solid carbon/molten electrolytemixed product is compressed directly on the cathode in the electrolysischamber. In addition, it is also noted that some product may be presenton both sides of the cathode, in which case product may also be directlycompressed between the press plate and the cathode, and separated andcollected.

Thus, as illustrated by the various embodiments, and as can beimplemented by any of the embodiments unless specifically notedotherwise, the invention concerns applying a force to a nanoscopicproduct to macroscopically separate material. The invention is typicallyapplied to a paste, and is especially useful for a paste product thatforms at the cathode during an electrolysis reaction, and comprises asolid carbon nanomaterial product bound with some of the liquidelectrolyte in which the reaction is performed (i.e., the paste is asolid carbon plus liquid electrolyte). When the paste is compressed, thebound liquid electrolyte is separated from the solid desired carbonnanomaterial product. The electrolyte is not diluted, destroyed orotherwise rendered unusable as a result of the separation process.Accordingly, the electrolyte can be recycled (e.g., returned to theelectrolysis chamber) or discarded, and the solid carbon productremains. These electrolysis reactions are performed in moltenelectrolytes at 700+degrees C. The compression can be performed in theelectrolysis chamber or outside the electrolysis chamber, and can bedone while the paste is on the cathode or after it is removed from thecathode. If the compression/separation process is performed in aseparate extraction chamber (i.e., not in the electrolysis chamber inwhich the reaction was carried out) the product can be cooled below themelting point of the electrolyte to form a solid carbon/solidelectrolyte product that can be removed from the cathode, placed in theseparate extraction chamber, then heated to re-melt the electrolyte sothe liquid electrolyte can be removed from the desired solid carbonproduct in that separate chamber.

Though a compression force is illustrated, other suitable forces can beapplied, such as a torque, centripetal force, twisting, or rotationalforce. And, while the invention is illustrated for use with a pasteproduct to separate electrolyte and carbon product, the system can beutilized for separating other suitable materials. In addition, thesystem utilized to apply the force to a product can be any suitableconfiguration, and the systems shown in the figures are only forillustrative purposes and do not limit the invention. For example, thefigures illustrate that any number of containers or chambers can beutilized. In FIG. 7, a single chamber can be utilized for electrolysis,compression and separation. In FIG. 4, a chamber is provided forcompression and separation that is separate from the chamber whereelectrolysis occurs. In FIG. 1, three chambers can be utilized forcompression and separation, and in FIG. 2 two chambers can be utilized.The chambers can be arranged horizontally or vertically, and can haveany suitable shape, such as for example rectangular, square andcircular. The force can be imparted by any suitable apparatus, such as apress plate and rod or hydraulic mechanism, pneumatically or manually.In addition, the type and manner of application of force can be varied,such as for example a compression force can be applied, removed, andthen applied again (and repeated), or a compression force can beapplied, followed by a difference force, such as torque. Still further,the compression can be applied while the product is on the cathode, orafter the product is removed from the cathode.

It is noted that high temperature presses might be thought to expose andoxidize (combust) the carbon product. However, the inventors recognizedthat the electrolyte itself protects the product from combustion duringthe pressing process. In addition, nanomaterials are too small to beseparated by presses since the presses intrinsically depend on greaterthan micron or greater than millimeter filters, and therefore thenanomaterials are too small to be separated by the filters. However, theinventors recognized that the agglomeration and aggregation of thecarbon nanotube product during electrolysis allows for filtering ofnanomaterials with larger filters, such as micron and millimeter sizedfilters. That is, the individual carbon nanomaterial product hasnanoscopic dimensions, but the carbon agglomerates, and the agglomeratedproduct has micron and millimeter dimensions.

In another embodiment of any of the processes described herein, theelectrolyte is removed through an interface with pores 108. In oneembodiment, the interface with pores 108 comprises a foam, such as, forexample, a porous carbon felt, a graphite felt, a metal mesh, a porousor sieve ceramic, or any combination thereof. In one embodiment, thepore size of the interface with pores is between about 10 μm and about10 mm, such as between about 0.1 mm and about 5 mm or between about 0.3mm and about 3 mm. In a further embodiment, any of the processesdescribed herein further comprises applying a vacuum, such as vacuum220, during the separation/extraction process, for example, to enhanceremoval of the electrolyte and separation of the solid carbon product

In another embodiment, an oxygen excluding gas (e.g., a gas that is freeor substantially free of oxygen), such as, for example, nitrogen, carbondioxide, argon, or a reducing gas, such as, for example, methane,ammonia, hydrogen and hydrogen sulfide, and any combination of any ofthe foregoing, is used to blanket the carbon product during theseparation, for example, to minimize any loss by oxidation of the carbonproduct during exposure to oxygen at elevated temperatures.

In other embodiments of any of the processes described herein, themolten electrolyte cathode product mix is compressed directly on thecathode in the electrolysis chamber.

In another embodiment of any of the processes described herein, theelectrolyte cathode product mix is removed from the cathode in theelectrolysis chamber, e.g. without pumping, into a separate extractioncompression chamber prior to separation of the solid product.

In further embodiments of any of the processes described herein, themixed product is separated without cooling from the molten stage, forexample, for reinclusion in the electrolysis without loss of heat. Infurther embodiments of any of the processes described herein, the mixedproduct is cooled, and the cooled congealed product is reheated abovethe electrolyte melting point prior to compression (separation). Ineither case, the molten mix may be compressed through the application ofpressure and pressed through the interface 108 with pores smaller thanthe carbon matrix size. The macroscopic (greater than micron) pore sizeis larger than the nm dimensions of nanomaterials in the carbon product,but smaller than the carbon matrix size. Product compression drawselectrolyte out of the product while solid carbon is restrained by thepores and retained in the product.

EXAMPLES Example 1: Extraction Using Vacuum

A solid carbon/molten electrolyte mixed product (carbonogel), removedfrom the cathode of a brass cathode and formed on the cathode byelectrolysis in a molten alkali carbonate electrolyte at 750° C. at anapplied current density of 0.1 A cm⁻² between an Inconel anode and thebrass cathode for 4 hours, was separated into carbon nanotubes and clearelectrolyte using the product extractor 300 shown in FIG. 2A. Carbonfelt was placed on a ⅛″ honeycomb structured steel plate that acts as asupport during the subsequent pressing stage. On top of the carbon felt,respective layers of 200×200, 100×100 and finally 50×50 Monel mesh wereplaced. Carbon dioxide flowed into the top of the extractor to preventoxidation of the carbonogel and subsequent separated carbon product. 50g of carbonogel product grown by electrolysis in a pure lithiumcarbonate electrolyte, and previously analyzed as containing 6% carbonnanomaterials and 94% electrolyte (comprising of 3 g of carbon and 47 gof electrolyte) was removed from the cathode and placed at 770° C. ontop of the uppermost (50 mesh) Monel layer. Above the carbonogel wasplaced subsequent layers of 40×40 Inconel mesh and 200×200 Monel mesh.The press plate shown on the left side of FIG. 2A was placed on top ofthe uppermost mesh layer and a pressure of 0.5 tonnes was applied for1.5 hours. A vacuum 304 of 0.08 MPa was applied through the metal tubeshown on the left side of FIG. 2A. The vacuum was applied in theelectrolyte collection chamber at the bottom of the extractor. Finally,the extractor was cooled, the press plate removed, the carbon productretained, and the clear extracted electrolyte removed and weighed. 87.0%of the electrolyte in the carbonogel was removed and recovered by thisprocedure.

Example 2: Extraction without Using Vacuum

A solid carbon/molten electrolyte mixed product (carbonogel), removedfrom the cathode of a brass cathode and formed on the cathode byelectrolysis in a molten alkali carbonate electrolyte at 750° C. at anapplied current density of 0.1 A cm² between an Inconel anode and thebrass cathode for 4 hours, was separated into carbon nanotubes and clearelectrolyte using the product extractor shown on the middle and rightsides of FIG. 2A. No carbon felt was used. Use of a larger pressminimized leakage at the press plate edges, and decreased the presstime, both improving extraction efficiency even in the absence of avacuum draw.

On the honeycomb structured steel support plate was placed respectivelayers of (1) 40×40 Inconel mesh, (2 and 3) two layers of 200×200 Monelmesh, and finally (4) another 40×40 Inconel mesh. Carbon dioxide flowedinto the top of the extractor to prevent oxidation of the carbonogel andsubsequent separated carbon product. 200 g of carbonogel product grownby electrolysis in a 20 wt. % sodium carbonate and 80 wt. % lithiumcarbonate electrolyte, and previously analyzed as containing 6% carbonnanomaterials and 94% electrolyte (comprising of 3 g of carbon and 47 gof electrolyte), was removed from the cathode and placed at 770° C. ontop of the uppermost mesh layer. Above the carbonogel was placedsubsequent layers of 40×40 Inconel mesh and 200×200 Monel mesh. Thepress plate was placed on top of the uppermost mesh layer and a pressureof 5 tons was applied for 0.5 hours. A vacuum of 0.08 MPa was appliedthrough the metal tube shown on the left side of FIG. 2A. The vacuumdraw was applied in the electrolyte collection chamber at the bottom ofthe extractor. Finally, the extractor was cooled, the press plateremoved, the carbon product retained and the clear extracted electrolyteremoved and weighed. 93.9% of the electrolyte in the carbonogel wasremoved and recovered by this procedure.

It is further noted that the description and claims use severalgeometric or relational terms, such as planar, elongated, circular,parallel, perpendicular, orthogonal, transverse, longitudinal, and flat.In addition, the description and claims use several directional orpositioning terms and the like, such as horizontal, vertical, top,bottom, left, right, up, down, distal, and proximal. Those terms aremerely for convenience to facilitate the description based on theembodiments shown in the figures. Those terms are not intended to limitthe invention. Thus, it should be recognized that the invention can bedescribed in other ways without those geometric, relational, directionalor positioning terms. In addition, the geometric or relational terms maynot be exact. For instance, walls may not be exactly perpendicular orparallel to one another but still be considered to be substantiallyperpendicular or parallel because of, for example, roughness ofsurfaces, tolerances allowed in manufacturing, etc. And, other suitablegeometries and relationships can be provided without departing from thespirit and scope of the invention.

The following documents are incorporated herein by reference.

(1) Ren et al., One-pot synthesis of carbon nanofibers from CO₂ , Nano.Let., 15, 6142-6148 (2015); (2) Johnson et al., Carbon nanotube woolsmade directly from CO₂ by molten electrolysis: Value driven pathways tocarbon dioxide greenhouse gas mitigation, Materials Today Energy, 5,230-236 (2017); (3) Ren et al., Tracking airborne CO₂ mitigation andlow-cost transformation into valuable carbon Nanotubes, ScientificReports, Nature, 6, 27760 1-10 (2016); (4) Wu et al., One-pot synthesisof nanostructured carbon material from carbon dioxide via electrolysisin molten carbonate salts, Carbon, 106, 208-217 (2016); (5) Wang et al.,Exploration of alkali cation variation on the synthesis of carbonnanotubes by electrolysis of CO2 in molten carbonates, J. CO ₂Utilization, 34, 303-312 (2019); (6) Liu et al., Carbon Nano-Onions MadeDirectly from CO₂ by Molten Electrolysis for Greenhouse Gas Mitigation,Advanced Sustainable Systems, 1900056, 1-10 (2019); (7) Yu et al.,Strength and Breaking Mechanism of Multiwalled Carbon Nanotubes UnderTensile Load, Science. 287, 637-640 (2000); (8) Chang et al., A NewLower Limit for the Ultimate Breaking Strain of Carbon Nanotubes, ACSNano, 4, 5095-5100 (2010); (9) Gui et al., Carbon nanotube sponges,Advanced Materials, 22, 617-621 (2010); (10) Wu et al., Carbon nanofiberaerogels for emergent cleanup of oil spillage and chemical leakage underharsh conditions, Scientific Reports, 4, 4079 1-6 (2014); (11) Kim etal., Graphene-Coated Carbon Nanotube Aerogels Remain Superelastic whileResisting Fatigue and Creep over −100 to +500° C., Chemistry ofMaterials, 4, 2748-2755 (2017).

The foregoing description and drawings should be considered asillustrative only of the principles of the invention. The invention maybe configured in a variety of shapes and sizes and is not intended to belimited by the embodiment. Numerous applications of the invention willreadily occur to those skilled in the art. Therefore, it is not desiredto limit the invention to the specific examples disclosed or the exactconstruction and operation shown and described. Rather, all suitablemodifications and equivalents may be resorted to, falling within thescope of the invention.

1. A process for preparing an aerogel by separating electrolyte from asolid carbon/molten electrolyte mixed product removed from the cathodeof a carbonate electrolysis, the process comprising: (i) applying aforce to compress the solid carbon/molten electrolyte mixed product toremove the electrolyte; (ii) removing the force; and (iii) isolating theaerogel.
 2. The process according to claim 1, wherein steps (i) and (ii)are repeated two, three or four times, prior to step (iii)
 3. Theprocess according to claim 1, wherein the compression is conducted at apressure of between about 10 psi and about 100,000 psi.
 4. The processaccording to claim 1, wherein the electrolyte is removed through aninterface with pores.
 5. The process according to claim 4, wherein theinterface with pores comprises a porous carbon felt, a graphite felt, ametal mesh, a porous or sieve ceramic, or any combination thereof. 6.The process according to claim 4, wherein the pore size of the interfaceis between about 10 μm and about 10 mm.
 7. The process according toclaim 1, wherein the process is conducted at a temperature between about399° C. and about 900° C.
 8. The process according to claim 1, whereinthe process further comprises applying a vacuum during the separationprocess.
 9. The process according to claim 8, wherein the process isconducted at a pressure between about 0.1 and about 0.9 atmospheres. 10.The process according to claim 8, wherein the process is conducted at apressure less than about 0.1 atmospheres.
 11. The process according toclaim 1, wherein the process is conducted under a gas that is free orsubstantially free of oxygen.
 12. The process according to claim 11,wherein the gas is selected from nitrogen, carbon dioxide, argon,methane, ammonia, hydrogen, hydrogen sulfide, and any combinationthereof.
 13. The process according to claim 1, wherein the mixed productis cooled after its formation by electrolysis and reheated prior to acompression step.
 14. The process according to claim 1, in which thesolid carbon/molten electrolyte mixed product is compressed directly onthe cathode in an electrolysis chamber.
 15. The process according toclaim 1, wherein the solid carbon/molten electrolyte mixed product ismoved from the cathode of an electrolysis chamber to an extractioncompression chamber prior to compression.
 16. The process according toclaim 1, wherein the electrolyte is not a flowing electrolyte.
 17. Theprocess according to claim 1, wherein the electrolyte is notrecirculated via a recirculation loop.
 18. The process according toclaim 1, wherein the aerogel has an average thickness greater than 1millimeter.
 19. The process according to claim 1, wherein the aerogelcomprises greater than about 80% carbon nano-materials. 20-21.(canceled)
 22. The process according to any one of claim 1, whereinsolid carbon product aerogel comprises greater than about 95% carbonnano-materials. 23-28. (canceled)
 29. The process according to claim 1,wherein the aerogel is formed from raw carbon nano-material thatagglomerates during the carbonate electrolysis and the isolatingcomprises filtering the aerogel with a filter having pores larger thanthe raw carbon nano-material.
 30. The process according to claim 1,wherein the solid carbon/molten electrolyte comprises a paste. 31-34.(canceled)
 35. A process for preparing a carbanogel comprising:incorporating a molten electrolyte into a porous solid carbon matrix.36. The process according to claim 35, wherein the carbanogel contains amajority of molten carbonate with an intermingled solid matrixcomponent.
 37. The process according to claim 35, wherein the solidcarbon matrix component comprises greater than about 80% carbonnanomaterials.
 38. The process according to claim 35, wherein the solidcarbon matrix component comprises greater than about 95% carbonnanomaterials.
 39. The process according to claim 1, wherein the aerogelcan be repeatedly compressed without detrimental effect on the structureand/or stability of the resulting aerogel.
 40. The process according toclaim 37, wherein the carbon nano-materials are carbon nanofibers,carbon nanotubes, carbon nano-onions, carbon nano-platelets, carbonnano-scaffolds, graphene or any combination thereof.
 41. A productcomprising: an aerogel having a majority of molten carbonate with anintermingled solid matrix component.
 42. The product of claim 41,wherein the aerogel comprises a carbanogel.
 43. The process according toclaim 35, wherein the carbanogel can be repeatedly compressed withoutdetrimental effect on the structure and/or stability of the resultingcarbanogel.
 44. A process for preparing a carbanogel on a cathode,comprising: electrolyzing a molten carbonate electrolyte by applying acurrent between the cathode and an anode immersed in the electrolyte.45. The process according to claim 19, wherein the carbon nano-materialsare carbon nanofibers, carbon nanotubes, carbon nano-onions, carbonnano-platelets, carbon nano-scaffolds, graphene or any combinationthereof.
 46. The process according to claim 22, wherein the carbonnano-materials are carbon nanofibers, carbon nanotubes, carbonnano-onions, carbon nano-platelets, carbon nano-scaffolds, graphene orany combination thereof.